Production and recovery of oxygenated hydrocarbons by plural distillation



OGL 31, 1967 R. c. BINNING ETAL 3,350,421

Y PRODUCTION AND RECOVERY OF OXYGENATED HYDROCARBONS BY PLURAL DISTILLATION Filed Feb. 12, 1964 BY ATTORNEY No Inu United States Patent O RECOVERY OF OXYGEN- HYDRCARBONS BY PLURAL DISTIL- LATION Robert C. Binning, St. Louis, Leon E. Bowe, Glendale,

and Harold R. Null, Florissant, Mo., assignors to Monsanto Company, a corporation of Delaware Filed Feb. 12, 1964, Ser. No. 344,494 4 Claims. (Cl. 2450-3485) 3 PRODUCTUN AND ATED ABSTRACT F THE DlSCLSURE The present invention relates to the production and recovery of commercially valuable chemicals. In broad aspect, the present invention relates to the production and recovery of aliphatic organic oxygenated compounds by the liquid phase oxidation of lower aliphatic hydrocarbons rich in olens. Another aspect of this invention relates to the non-catalytic liquid phase oxidation of oleiins with molecular oxygen and recovery of the more valuable oxidation products. In one preferred aspect, the present invention relates to the non-catalytic direct oxidation of propylene with molecular oxygen in a unique liquid phase, described hereinafter, and the recovery of valuable oxidation products. In its most preferred aspect the present ininvention relates to the controlled non-catalytic, direct oxidation of propylene with molecular oxygen in a liquid phase comprising fully esteriied polyacyl esters of polyols, and to the recovery of propylene oxide and acetic acid as the primary product species, and other oxidation products such as acetaldehyde, methyl formate, etc.

A particular feature of this invention is the ilexibility of the oxidation process which can be controlled to produce greater or lesser yields of the desired commercially Valuable end products (s) relative to each other. Another aspect of the feature just mentioned is the controllability of the process to produce and recover maximum yields of commercially valuable products, while minimizing yields of less-valuable oxygenated products of the reaction. The commercial value of such flexibility in a hydrocarbon oxidation process is apparent. For example, at any one time there may be great commercial demand for a particular product of the oxidation, say, propylene oxide, while at the same time the demand for another product of the reaction, say acetic acid, is low. According to the present invention, the oxidation is controllable to produce a minimum of acetic acid and a maximum of propylene oxide. The reverse situation is likewise true. Alternatively, where commercial demand warrants it, the present process is controllable to produce maximum yields of propylene oxide and acetic acid at the expense of other less valuable oxidation products, but not of each other.

In the liquid phase oxidation of aliphatic hydrocarbons such as olens and parans or mixtures of these with molecular oxygen, a great variety of oxygenated products are produced, eg., acids, alcohols, aldehydes, esters,

ketones, epoxides, glycols, etc. A 4great amount of research etlort has been expended in attempts to develop cornmercially feasibly hydrocarbon oxidation processes. These research eorts Ihave been divided generally into two categories, viz., (1) hydrocarbon oxidation reactions, per se, which seek to determine operable and optimum conditions for oxidizing specilic hydrocarbons to specific oxygenated products and (2) specific recovery systems for various of the myriad oxidation products.

In order to illustrate typical prior art approaches to hydrocarbon oxidation and product recovery processes, the discussion below is an attempt to illustrate the problems encountered as well as to set the background for the present invention.

Since the present invent-ion is concerned with a novel liquid phase hydrocarbon oxidation and product recovery system, the discussion below will be directed to typical existing prior art schemes for liquid phase hydrocarbon oxidation and product recovery systems. These prior art processes describe a variety of approaches to a proper balancing of a series of reaction variables in order to obtain the desired oxygenated product, e.g., epoxides, alcohols, acids, esters, etc. For example', various specific oxidation catalysts, catalyst-solvent, or catalyst-promotersolvent systems have been described (U.S. patents solvent systems have been described (U.S. patents 2,741,- 623, 2,837,424, 2,974,161, 2,985,668, and 3,071,601); another approach is the incorporation of oxidation anti-catalysts which retard certain undesirable side reactions (U.S. Patent 2,279,470); still another approach emphasizes the use of water-immiscible hydrocarbon solvents alone, or in the presence of oxidation catalysts and/or polymerization inhibitors such as nitrobenzene (U.S. Patent 2,780,665); or in the presence of saturated hydrocarbons (=U.S. Patent 2,780,634); another method describes the use of neutralizers such as alkali metal and alkaline earth metal hyd-roxides, or salts of these metals (U.S. Patent 2,838,524); another approach involves the use of certain catalysts in an alkaline phase (U.S. Patent 2,366,724), or a liquid phase maintained at specified critical pH values (U.S. Patent 2,650,927); and still other approaches emphasize criticality of oxygen pressure (U.S. Patent 2,879,276), or the geometry of the reaction zone (U.S. Patents 2,530,509 and 2,977,374). The foregoing represent prior art approaches to problems encountered in the utilization of a liquid phase in hydrocarbon oxidation processes.

While the addition of various additives in some prior art processes may accomplish the purpose for which they were used, e.g., neutralization of acid by addition of alkaline substances, the additives themselves introduce other problems and disadvantages into a process. For example, in the liquid phase oxidation of olens with molecular oxygen, organic acids, such as acetic and formic acids, are formed. The latter acid, in substantial quantities, is recognized as being deleterious -in the reaction. Hence, prior art elTorts have 'been directed to selectively removing the deleterious formic acid from the relatively innocuous acetic (or other organic acids) or to the removal of all acidic components from the reaction mixture. Commonly, these acids are neutralized by the addition of alkaline materials to the main oxidation reactor and/or to auxiliary acid extraction vessels. Typical alkaline materials added include alkali metal hydroxides and carbonates, alkaline earth oxides, hydroxides and carbonates, mildly basic heavy metal hydroxides, ammonium hydrates and metal hydrates, salts of weak acids, e.g., acetic acid and other carboxylates such as metal salts of tartaric, stearic, oleic and palmitic acids. However, the use of these `basic materials presents additional process problems. For example, many alkaline materials form insoluble salts with the organic acids and as these salts continue to accumulate, control of the main oxidation reaction is rendered more difficult. Consequently, salt removal systems, e.g., lters, evaporators, crystallizers, solvent extractors and the like, must be incorporated into the process apparatus. On the other hand, use of soluble alkaline substances leads to the formation of colored or resinous materials which cause gumming of apparatus components.

It is, therefore, an object of the present invention to provide a liquid phase hydrocarbon oxidation process for the production and recovery of valuable oxygenated products, which process is free of numerous limitations recited in prior art processes.

An object of this invention is to provide a noncatalytic direct oxidation of olen-rich hydrocarbon mixtures with molecular oxygen in a liquid phase comprising fully esteried polyacyl esters of polyols to produce and recover valuable oxygenated products.

A further object of the present invention is the elimination of numerous apparatus components heretofore required in separation and rening trains for the recovery of propylene oxide, acetic acid and other oxygenated products produced in the direct oxidation of olens.

Another object of this invention is to provide a controlled hydrocarbon oxidation process to obtain specific product distributions and ratios.

A further object of this invention is to provide a liquid phase propylene oxidation process for the controlled production and recovery of propylene oxide, acetic acid an other valuable oxygenated products, which process is not dependent upon the presence or absence of any catalyst; nor is it dependent upon the presence of water-immiscible solvents or upon solvents containing added buffers or acid neutralizers or other additives or secondary treatments with alkaline materials to remove acidic components; nor is it dependent upon the presence of saturated compounds, initiators, promoters or anticatalysts; further, it is not dependent upon critical pH levels of the reaction mixture or geometries.

These and other objects will become apparent as the description of the invention proceeds.

The invention will be more fully understood by reference to the accompanying drawing which constitutes a part of the present invention.

In the gure is shown a diagrammatic tlow sheet illustrating a preferred embodiment of the invention.

The present invention comprises the production of propylene oxide, acetic acid and other valuable oxygenated products by the controlled direct oxidation of propylene with molecular oxygen in the liquid phase, and to a novel means of separating and recovering these products.

The liquid phase in which the oxidation occurs comprises solvents which are essentially chemically indifferent, high boiling with respect to volatile oxidation products and are oxidatively and thermally stable under the condition of the reaction described. Further, the solvents employed in the present invention are highly resistant to attack by free radicals which are generated in the oxidation process. Moreover, the solvents employed in the instant invention are effective in assuaging the deleterious effects of acidic components, especially formic acid and to a lesser degree acetic acid, on non-acidic co-products, e.g., propylene oxide, which are formed in the oxidation of olens. This assuaging eiect is achieved, in part, by a proton solvation of the acidic components by the solvent which results in an acid-leveling which, in turn, permits substantially complete retention of the propylene oxide formed in the oxidation.

Solvents primarily and preferably contemplated herein comprise fully esteried polyacyl esters of polyhydroxyalkanes, polyhydroxycycloalkanes, polyglycols and mixtures thereof. Polyacyl esters contemplated herein contain, generally, from l to 18 carbon atoms in each acyl moiety and from 2 to 18 carbon. atoms in each alkylene or cycloalkylene moiety. However, best results obtain when the acyl moiety contains from l to 6 carbon atoms and the alkylene and cycloalkylene moiety each contains from 2 to 6 carbon atoms. These esters may be readily prepared by methods known to the art. For example, in U.S. Patent No. 1,534,752 is described a method whereby glycols are reacted with carboxylic acids to produce the corresponding glycol ester. Acid anhydrides may be used in place of the acids.

Representative glycols include straight-chain glycols, such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, decylene glycol, dodecylene glycol, pentadecylene glycol and octadecylene glycol. Branched-chain glycols such as the iso, primary, secondary and tertiary isomers of the above straight chain glycols are likewise suitable, c g., isobutylene glycol, primary, secondary, and tertiary amylene glycols, Z-methyl- 2,4-pentanediol, 2ethyl-l,3hexanediol, 2,3-dimethyl-2,3 butanediol, 2-methyl-2,3butanediol and 2,3-dimethyl-2,3 dodecanediol. Polyalkylene glycols (polyols) include diethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and dihexylene glycol.

In addition to straight and branched-chain glycols, alicyclic glycols such as 1,2-cyclopentanediol, 1,2-cyclohexanediol, l-rnethyl-1,2-cyclohexanediol and the like may be used.

Other suitable hydroxy compounds include polyhydroxy alkanes, such as glycerol, erythritol and pentaerythritol and the like.

Representative carboxylic acids include fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valerie acid, caproic acid, caprylic acid, lauric acid, palmitic acid, stearic acid, naphthenic acids, such as cyclopentane carboxylic acid, cyclohexane carboxylic acid, and aromatic acids such as benzoic acid and the like.

Representative polyacyl esters include polyacyl esters of polyhydroxy alkanes, such as triacyl esters of glycerol, .g., glycerol triacetate; tetraacyl esters of erythritol and pentaerythritol, e.g., erythritol tetraacetate and pentaerythritol tetraacetate and the like, and polyacyl esters of polyalkylene glycols (polyglycols), such as diethylene glycol diacetate, dipropylene glycol diacetate, tetraethylene glycol diacetate and the like. These polyacyl ester solvents rnay be used individually or as mixtures, being compatible with each other. For example, a mixture of varying proportions of a diacyl ester of a hydroxyalkane, such as propylene glycol diacetate, and a polyacyl ester of a polyglycol, such as dipropylene glycol diacetate, may be used. Or, a mixture of a polyacyl ester of a polyglycol, such as dibutylene glycol dibutyrate, and a polyacyl ester of a polyhydroxy alkane, such as glycerol trivalerate, or pentaerythritol tetrapropionate may be used as the solvent in the instant process illustrated in the examples below.

Of particular interest in the present process are the vicinal diacyl esters of alkylene glycols, such as the dirformates, diacetates, dipropionates, dibutyrates, divalerates, dicaproates, dicaprylates, dilaurates, dipalmitates and distearates, and mixtures thereof, of the alkylene and polyalkylene glycols recited above. Still more particularly, of greater interest are the diacetates of ethyl-l ene and propylene glycols used individually or in admixtures of any proportion.

Polyacyl esters having mixed acyl groups are likewise suitable, e.g., ethylene glycol formate butyrate, propylene glycol acetate propionate, propylene glycol butyrate propionate, butylene glycol acetate caproate, diethylene glycol acetate butyrate, dipropylene glycol propionate caproate, tetraethylene glycol butyrate caprylate, erythritol diacetate dipropionate, pentaerythritol dibutyrate divalerate, glycerol dipropionate butyrate and cyclohexanediol acetate valerate.

Monoacyl esters of polyhydroxyalkanes and polyglycols are unsuitable for use as a reaction medium according to the present process. The same is true of other hydroxy or hydroxylated compounds such as glycerine, glycols, polyglycols and hydroxy carboxylic acids. This is due to the presence of an abundance of reactive hydroxyl groups which are susceptible to autooxidative attack, hence, introduce a concomitant oxidation side reaction which competes with the desired direct oxidation of the olefin, and too, these hydroxyl groups when esteried with organic acids present, produce water which together with water normally lformed in the reaction provide quantities suficient to inhibit the oxidation of the olefin to the olefin oxide and/or to hydrolyze the olefin oxide present.

In the preferred mode of operation the polyacyl esters used herein constitute the major proportion of the liquid medium with respect to all other constituents including reactants, oxidation products and co-products dissolved therein. By major is meant that enough solvent is always present to exceed the combined weight of all other constituents. However, it is within the purview of this invention, although a less preferred ernbodiment, to operate in such manner that the combined weight of all components in the liquid phase other than polyacyl esters exceeds that of the polyacyl ester solvent. For example, a renery grade hydrocarbon feedstock or a crude hydrocarbon feedstock containing, e.g., 50% by weight of the olefin to be oxidized, c g., propylene, and 50% by weight of saturated hydrocarbons, e.g., an alkane such as propane, may be used in quantities up to 50% as acetone and methyl acetate, and high -boilers (components having boiling points higher than that of the polyacyl ester solvent) formed in the reaction and/or recycled to the reactor may constitute as much as 75% by weight of the liquid reaction medium, according to reaction conditions or recycle conditions.

When carrying out the invention according to the less preferred mode of operation, the quantity of polyacyl ester solvent present in the liquid reaction medium should be not less than by weight of said medium in order to advantageously utilize the aforementioned benefits characteristic to these unique olefin oxidation solvents.

In further embodiments of the present invention for oxidizing olefins with molecular oxygen in the liquid phase, the polyacyl ester solvents are suitably used in combination with diluents or auxiliary solvents which are high boiling with respect to volatile oxidation products, are relatively chemically indifferent and oxidatively and thermally stable under reaction conditions. Here, too, the polyacyl ester solvents should be utilized in quantities not less than 25% by weight of the liquid reaction medium in order to retain the superior benefits of these polyacyl ester solvents in liquid phase olefin oxidations.

Suitable diluents which may be utilized with the polyacyl ester solvents of this invention include, e.g., hydrocarbon solvents such as xylenes, kerosene, biphenyl and the like; halogenated benzenes such as chlorobenzenes, e.g., chlorobenzene and the like; dicarboxylic acid esters such as dialkyl phthalates, oxalates, malonates, succinates, adipates, sebacates, e.g., dibutyl phthalate, dimethyl succinate, dimethyl adipate, dimethyl sebacate, dimethyl oxalate, dimethyl malonate and the like; aromatic ethers such as diaryl ethers, e.g., diphenyl et-her; halogenated aryl ethers such as 4,4dichlorodiphenyl ether and the like; diaryl sulfoxides, e.g., diphenyl sulfoxide, dialkyl and diaryl sulfones, eg., dimethyl sulfone and dixylyl sulfone and nitroalkanes, e.g., nitrohexane. While the foregoing have been cited as typical diluents which may be used in combination with the polyacyl ester solvents in this invention, it is to be understood that these are not the only diluents which can be used. In fact, the benefits accruing from the use of these polyacyl esters can be utilized advantageously Vwhen substan- 6 tially any relatively chemically indifferent diluent is combined therewith.

Therefore, the present invention in its broadest -use comprehends the oxidation of olefin-containing feedstocks in a liquid reaction medium consisting essentially of at least 25% by weight based on said medium of at least one fully esterified polyacyl ester described above, and recovery of valuable oxygenated products.

In any case, the liquid reaction medium referred to herein is defined as that portion of the total reactor content which is in the liquid phase.

It is therefore apparent that the liquid reaction media contemplated herein possess not only those characteristics described in prior art solvents, viz, they are high boiling Wit-h respect to volatile oxidation products under the conditions of reaction, essentially chemically indifferent and oxidatively and thermally stable, but in addition, possess characteristics not described in prior art oxidations, viz, resistance to free radical attack, the ability to reduce and/or eliminate the deleterious effects of acidic components by proton solvation and/or ester interchange. In addition, due to the facile manner in which the present oxidation proceeds in the described solvents, no oxidation catalysts, promoters, initiators, buffers, neutralizers, polymerization inhibitors, etc. are required as in many prior art processes.

As noted above, no added catalysts are required in the present oxidation process. However, due to the versatility of the above-described solvents in olefin oxidations, the usual oxidation catalysts can be tolerated although usually no significant benefit accrues from their use. For example, metalliferrous catalysts such as platinum, selenium, vanadium, iron, nickel, cobalt, cerium, chomium, manganese, silver, cadmium, mercury and their compounds, preferably in the oxide form, etc., may be present in gross form, supported or unsupported, or as finely divided suspensions.

In like manner, since the olefin oxidations according to this invention proceed at a rapid rate after a brief induction period, no initiators or promoters are required, but may be used to shorten or eliminate the brief induction period, after which no additional initiator or promoter need be added.

Suitable initiators include organic peroxides, such as benzoyl peroxide; inorganic peroxides, such as hydrogen and sodium peroxides; peracids, such as peracetic and perbenzoic acids; ketones, such as acetone; ethers, such as dicthyl ether; and aldehydes, such as acetaldehyde, propionaldehyde and isobutyraldehyde.

Use of the solvents described herein being free of the necessity to use various additives described in prior art processes, enhances the separation and recovery of propylene oxides by the sequence of steps described in detail below.

In carrying out the process of the instant invention, the reaction mixture may be made up in a variety of ways. For example, the olefin and oxygen may be pre-mixed with the solvent and introduced into the reactor, or the olefin may be premixed with the solvent (suitably, up to 50% by weight based on the solvent and, preferably, from 5 to 30% by Weight based on the solvent). Preferably, the olefin is pre-mixed with the solvent and the oxygen-containing gas introduced into the olefin-solvent mixture incrementally, or continuously, or the olefin and oxygen-containing gas may be introduced simultaneously through separate or common fcedlines into a body of the solvent in a suitable reaction vessel (described below).

" oxygen input is adjusted in such manner as to prevent an excess of oxygen l%) in the off-gas or above the reaction mixture. Otherwise, a hazardous concentration of explosive gases is present. Also, if the oxygen (or air) feed rate is too high the olefin will be stripped from the mixture, thus reducing the concentration of olefin in the liquid phase and reducing the rate of oxidation of the olefin, hence giving lower conversions per unit time.

Intimate contact of the reactants, olefin and molecular oxygen in the solvent yis obtained by various means known to the art, e.g., by stirring, shaking, vibration, spraying, sparging or other vigorous agitation of the reaction mixture.

The olefin feed stocks pure propylene, mixtures of eg., ethylene, or olefin stocks containing as or more of saturated compounds, e.g., propane. Olefinic feed materials include those formed by cracking hydrocarbon oils, paraffin wax or other petroleum fractions such as lubricating oil stocks, gas oils, kerosenes, naphthas and the like.

The reaction temperatures and pressures `are subject only to those limits outside which substantial decomposition, polymerization and excessive side reactions occur in liquid phase oxidations of propylene with molecular oxygen. Generally, temperatures of the order of 50 C. to 400 C. are contemplated. Temperature levels sufficiently high to prevent substantial build-up of any hazardous peroxides which form are important from considerations of safe operation. Preferred temperatures are within the range of from 140 C. to 250 C. Still more preferred temperatures are within the range of from 160 C. to 210 C. Suitable pressures herein are within the range of from 0.5 to 350 atmospheres, i.e., subatmospheric, atmospheric or superatmospheric pressures. However, the oxidation reaction is facilitated by use of higher temperatures and pressures, hence, the preferred pressure range is from to 200 atmospheres. Still more preferred pressures are within the range of from 25 to 75 atmospheres. Pressures and temperatures selected will, of course, be such as to maintain a liquid phase.

The oxidation of olefins, e.g., propylene, in the present process is auto-catalytic, proceeding very rapidly after a brief induction period. A typical oxidation of propylene in a batch run requires from about l to 20 minutes. Similar, or faster, reaction rates obtain in continuous operation, e.g., as low as 0.1 min. reactor residence time.

The reaction vessel may consist of a wide variety of materials. For example, aluminum, silver, nickel, almost any kind of ceramic material, porcelain, glass, silica and 'various stainless steels, e.g., Hastelloy C, are suitable. It should be noted that in the instant process where no added catalysts are necessary, no reliance is made upon the walls of the reactor to furnish catalytic activity. Hence, no regard is given to reactor geometry to furnish largesurface catalytic activity.

The oxidation products are removed from the reactor, preferably, as a combined liquid and gaseous mixture, or the liquid reaction mixture containing the oxidation products is removed to a products separation system, a feature of which comprises in combination a flasher-stripper letdown arrangement. This arrangement in combination with the preceding propylene oxidation reaction and with succeeding product-separation steps constitutes a unique, safe, simple, economic and practical process for the cornmercial production and recovery of olefin oxides.

In regard to the `flasher-stripper let-down system, principal advantages accruing from its use are that the system simultaneously (l) utilizes the heat of the oxidation reaction in the initial separation of gaseous and liquid products; this eliminates the need of cooling the reactor effiuent, (2) minimizes the amount of overhead solvent consistent with the maximum amount of olefin oxide, e.g., propylene oxide (RO.) all of which goes overhead; (3) minimizes the amount of total overhead solvent, resulting in a reduced solvent load on subsequent distillation colcontemplated herein include propylene with other olefins, much as 50% umns. The advantages of this reduced solvent load are that smaller columns are required for the requisite products separations; (4) reduces to trace amounts the quantity of acidic components (most importantly, formic acid) in solvent recycle streams, and (5) removes the bulk of the fixed gases and very volatile components, thus reducing the pressure requirements to prevent excessive loss of products in subsequent processing steps.

A particular feature of the iiasher-stripper let-down combination is that in the flasher an initial separation of about one-third of the :acids formed in the reaction is accomplished and these are taken overhead', and by use of a stripping column for treatment of the asher bottoms, substantially all of the remaining acids, i.e., all but about 0.05 to 0.2 wt. percent based on the recycle stream are removed from the recycle solvent. Advantages afforded by such clean separation of acid values, particularly highly corrosive formic acid, from the recycle solvent are that all equipment forv processing the stripper bottoms can now be made of plain inexpensive carbon steel, replacing very expensive corrosion resistant stainless steels such as Hastelloy C, and the like, hitherto required. The economic advantages are manifest. Additionally, acids such as formic acid which are known to have an adverse effect upon the yield of olefin oxides in the primary oxidation reaction, as discussed above, are no longer made available, by means of recycle solvent in quantities sufficient to exert a deleterious effect on olefin oxide yield.

The total effect of the foregoing advantages is to provide an efficient, rapid economical method for stabilizing the propylene oxide reaction mixtures while unloading solvent from the oxidation products and recycling solvent to the reactor.

in contrast to the fiasher-stripper combination used herein the use of individual fiashers or distillation columns in the initial separation of the products from tlihe reactor etiiuent is inadequate for various reasons. For example, a single tiasher cannot simultaneously minimize the quantity of overhead solvent, hence reducing the liquid load in the distillation columns in the separation train, while minimizing the amount of propylene oxide in the bottoms stream recycled to the main reactor. If conditions of temperature and pressure in a single flasher are so adjusted as to permit the desired amount of solvent to go overhead, a large amount of acids (l5 wt. percent or more) appear in the bottoms stream and are recycled to the reactor. Moreover, in using a single asher substantial quantities of propylene oxide (on the order of 3040% of that produced) are taken as bottoms and recycled to the reactor thus reducing total yield, whereas in the present iiasher-stripper combination virtually all of the formed propylene oxide is removed from the recycle stream.

Further, when a single distillation column is used in the initial gas-liquid separation of reactor effluent this column must be approximately five times as large in cross sectional area as that column used herein into which the combined overhead streams of the fiasher and stripper are fed. In feeding the gas-liquid effluent directly into a distillation column a large amount of fixed gases are present, thus reducing plate efficiency and requiring additional plates `which materially adds to the cost of operation. A further disadvantage of having large quantities of fixed gases in a distillation column adjacent to the reactor is that much higher pressures and refrigerants (as opposed to cooling water) are required to condense overhead gases.

On the other hand, use of a plurality of distillation or stripping columns to effect an initial gas-liquid separation of the reactor effiuent is disadvantageous primarily because of the required increase in product hold-time in these columns. This increased hold-time necessitates longer exposure of the desired propylene oxide to the deleterious action of formic acid and/or undesired secondary reactions with co-products as by hydrolysis, esterification,

polymerization or decomposition. In addition, when no ashers are used the total reactor eluent is loaded into these -distillation columns thus requiring equipment of increased capacity and separation eciency. Elimination of a flasher, moreover, increases capital outlay since distillation columns are much more expensive than ashers.

The flasher-stripper let-down combination used herein is in like manner superior tol let-down arrangements comprising a plurality of flashers for a number of reasons. Primarily, by use of a ilasher-stripper combination greater control and flexibility of process operation is assured, it being much easier to change product separation specifications and operations in a stripper than in a iiasher. This is accomplished principally by controlling the heat input to the stripper from a reboiler. Since a flasher has only one equilibrium stage, a stripper magniies by several stages, depending upon the number and efficiency of plates therein, the degree of separation of products achieved by flashers. Another advantage of the iiasherstripper arrangement herein over the use of plural flashers is that using, e.g., a two-dasher let-down arrangement an undesirable amount of propylene oxide (on the order of 7-8% of that produced) is recycled to the main oxidation reactor, thus reducing total yield. On the other hand, using the asher-stripper combination described herein virtually all of the propylene oxide is separated Ifrom refurther advantage of using a stripper in place of a second flasher is that the former removes all but a small amount, i.e., approximately 0.05 to 0.2 wt. percent, based on total recycle stream, of formed acids from the recycle solvent, whereas -by use of ila'shers about 1-2 wt. percent of acids remain in the recycle solvent.

Bottoms from the stripper containing the bulk of the solvent and residue, i.e., components having boiling points above that of the solvent, are fed to the top of an absorber to ilow downward counter-currently to a stream of uncondensed materials from the ilasher and stripper overfed to a lower region of the absorber.

An important feature of this invention includes a residue removal column operating on a side stream of the solvent bottoms from the stripper. The material referred to as residue comprises polymeric components having a variety of functional groups including carboxyl, carbonyl, alkoxy and hydroxyl groups. When this residue is recycled to the main oxidation reactor it tends to build up to a level Wh1ch impedes the oxidation of propylene to desired end product, by competing with the propylene for the available oxygen. Therefore, by means of the residue removal column these high boiling polymers can readily be purged from the recycle solvent to maximize the yield of propylene oxide. On the other hand, by reducing the amount of residue purged from the recycle solvent these polymers can be recycled to the oxidation reactor and oxidized to yield other valuable products such as acetic acid. Thus, by means of this residue removal column the residue content in the recycle solvent can be regulated and, hence, the oxidation in the main oxidation reactor can be controlled to obtain greater yields of the desired end product(s) and/or any given product distribution and ratio.

A further advantage of the use of the residue removal column is that by purging residue from the solvent bottoms from the stripper Abefore entering the absorber, the absorbing capacity of the absorber is greatly increased. Thus, the solvent bottoms from the absorber are recycled to the main oxidation reactor substantially free of xed gases and residue (when desired).

The overhead from the asher and stripper is passed to condensers from which a stream of condensables is passed to a primary product splitter from which acids, water, intermediate boilers and residual solvent are removed as bottoms and an overhead stream containing propylene oxide and lower boiling components is removed overhead and passed to a C3 removal zone. The C3 removal zone serves to separate propylene and propane overhead -from propylene oxide, methyl formate and acetaldehyde which are removed as bottoms. The propylene may be separated from the propane and the former recycled to the reactor or, alternatively, the entire overhead from the C3 removal column processed as described below.

Bottoms from the aldehyde, methyl formate and propylene oxide are fed t0 distillation column. In the extractive distillation column, propylene oxide is selectively separated from methyl formate by means of a hydrocarbon entraining agent more fully described below. Methyl formate goes overhead while the hydrocarbon solvent containing propylene oxide is removed as bottoms from the extractive distillation column and fed to a propylene oxide rening zone where purified propylene oxide is stripped from the solvent and taken overhead while the hydrocarbon solvent is removed as bottoms and recycled to the extractive distillation column.

values, water and the remaining intermediate boilers, i.e., those not removed in the primary products splitter overhead stream, including methanol, methyl acetate, acetone, isopropanol, allyl alcohol, biacetyl and others, is directed to a solvent-acids splitter where most of the residual solvent is removed as bottoms and recycled to the reactor via the absorber. Overhead from the solvent-acid splitter containing the remaining residual solvent, water, acid values and intermediate yboilers is passed to an acids-intermediates separation column where the intermediate boiling components are recovered overhead. These intermediates may be separated into fractions suitable for various solvent utilities, e.g., a methanol, methyl acetate, acetone fraction is useful as a paint thinner or as a lm castingsolvent. Alternatively, these intermediates may be separated into individual components such as those mentioned above by various extraction means such as selective adsorption and fractional desorption, extractive distillation, azeotropic distillation, solvent extraction, etc., using a suitable extractant. Bottoms from the intermediate removal column containing water, formic acid, acetic acid and residual solvent are passed to an azeotropic distillation col-umn containing benzene. In this column benzene forms azeotropes with water and with formic acid which are taken overhead to a condenser cooled with circulating water. Upon condensing, water and formic acid are cleanly separated from benzene, and collected in a separator from which benzene is recycled to the azeotropic distillation column, while water and formic acid are removed as bottoms from the separator. Bottoms from the azeotropic distillation column comprising essentially acetic acid and residual solvent from the main oxidation reactor are passed to an acetic acid refining column from which purified acetic acid is removed overhead While the residual solvent is removed as bottoms and recycled to the absorber.

A preferred specific embodiment of the present invention will be described with reference to the accompanying drawing in connection with the direct oxidation of propylene in a continuous operation, and a specific novel method of separating and rening valuable oxygenated products including propylene oxide, acetic acid, acetaldehyde and methyl formate formed in the reaction. Suitable variations in the separation trains are also disclosed. Such conventional equipment as motors, pumps, valves, gauges, reux condensers, re-boilers, safety heads and the like are not shown in the drawing, but their inclusion is a variation readily apparent to those skilled in the art.

1. 1 Example 1 In this process a one-liter Magnedrive autoclave serves as the reactor portion of a continuous system. Solvent, propylene and oxygen are introduced through a bottom port directly below a Dispersimax turbine agitator operating at 1500 r.p.m. to obtain efficient mixing and internal gas recycle. The reactor is heated electrically and temperature control is maintained by modulating water ow through internal cooling coils. Reaction temperatures are continuously recorded on a strip-chart.

In operation the reactants, 92% propylene and 95% oxygen, together with propylene glycol diaoetate, a preferred solvent, are fed to the base of reactor 11, operating at 850 p.s.i.g. and 170 C. The molar feed ratio of C3H6/O2 is about 2.0. Total hold time is about 8 minutes. A variation is to provide two or more reactors in parallel operating under identical conditions and feeding the efiiuent from these reactors into the flasher-stripper letdown system described below.

The reaction product, a combined gas-liquid efiiuent is comprised of some fixed gases; low boiling components including unreacted propylene, propane, acetaldehyde, methyl formate, propylene oxide, etc.; va-rious intermediate boiling components, i.e., compounds boiling in the general range between the boiling points of propylene oxide and acetic acid, including some alcohols, e.g., methanol, isopropanol and allyl alcohol, some esters, eg., methyl acetate, acids, such as formic and acetic acids; acetone, water and various higher boiling components including acetonyl acetate, propylene glycol and some monoand diesters thereof such as propylene glycol monoformate, monoacetate, diformate and acetate formate. The largest fractions by weight of the reactor efliuent, however, are the solvent, propylene glycol diacetate, comprising about 49 weight percent, and a residue of polymeric material boiling above the solvent and comprising about 26 weight percent of the efiiuent stream.

The reactor eiiiuent is fed continuously to flasher 13 which operates at 165 p.s.i.a. pressure and is heated to 190 C. at the bottom and 170 C. at the top. From this asher most of the low and intermediate boiling components including all unreacted propylene, CO2 and at least one-half, and in this example approximately 65%, of the propylene oxide goes overhead along with about onefourth of the acids, e.g., formic and acetic acids, all dissolved gases and about 6-8% -of solvent. Bottoms from iiasher 13 are fed to stripping column 18 operating at approximately 24.7 p.s.i.a. and 200 C. at the bottom and using 6 distillation plates. The residual propylene oxide, i.e., generally between 30% and 50% of that formed, and about 33% in this example, substantially all of the remaining acids, lighter components and -15% of the solvent are vaporized and taken overhea Bottoms from stripper 18 containing the bulk of the solvent are fed through line 19 to absorber 20. A side stream 21 of the solvent efiiuent from stripper 18 is fed to residue removal stripper column 22 where residue, i.e., reaction products having boiling points above that of the solvent, is removed as bottoms and the solvent is removed overhead through line 23 and fed to the absorber via stripper bottoms stream 19, thus increasing the absorbing capacity of absorber 20. Column 22 is heated to about 153 C. at the top and 210 C. at the bottom at a pressure of 250 mm. Hg absolute. Seven distillation plates are used in the residue removal column.

In the present embodiment, the conditions of reaction tare established to produce a predetermined propylene oxide-acetic acid ratio, viz about 4.3. Under these conditions a definite amount of residue is required in the reactor (about 26 weight percent based on the .reactor efliuent). Hence, the amount of residue purged is such as to maintain this residue level constant in the reactor for the desired product distribution.

After passing through the absorber the solvent recycle stream is returned to the reactor through line 44. The

composition of the bottoms stream from the absorber iS comprised chiefly of about 55% propylene glycol diacetate solvent', about 29% residue; about 8.5% unreacted propylene and the balance oxygenated coproducts.

Whenever the quantity of residue entering the reactor by way of the solvent recycle stream is less than that leaving the reactor there is a net gain in residue content in the system. Thus, according to the present process appropriate adjustments must be made in the recycle solvent composition in order to prevent a buildup of residue in the system. Accordingly, a greater amount of recycle solvent is fed to the residue removal column to purge excess residue over that required for a given product distribution. Upon reaching steady state it is found that the residue content in the solvent recycle stream has .reached a level equivalent to the amount of residue leaving the reactor. In making these adjustments the product distribution is altered to produce the desired ratios of final products.

An -additional benefit of this invention is that the residue material itself is a useful product. This residue, e.g., can be hydrogenated, using ordinary hydrogenation catalysts to form ethers and ether-esters useful as lubricants, and/ or alcohols useful in polyurethane formulations, etc.

Overhead from flasher 13 and stripper 18 are directed to partial condensers 15 and 14, respectively, operating with cooling water. In condenser 15 uncondensables, including fixed gases, most of the CO2, about 7% of the total propylene oxide, about 74% of the unreacted propylene, and propane are separated from the condensables and fed through line 16 countercurrently to the solvent bottoms from stripper 18 to absorber 20. The uncondensables from condenser 14 containing CO2, propane and propylene are either discarded if desired or, optionally, compressed in compressor 24 and fed to the absorber via line 16 to recover the propylene. Absorber 20 operates at 150 p.s.i.g. and at temperatures of approximately 75 C. at the top and 95 C. at the bottom and has twenty-five plates. Fixed gases, O2, H2, N2, CH4, CO and CO2 are vented from the top of the absorber. Propane, propylene, propylene oxide and other soluble components are absorbed in the solvent which is recycled to the reactor through line 44 or, alternatively, further processed for propylene purification, as will be discussed below.

The condensed liquids from condenser 14 are combined with those from condenser 15 and this combined stream containing of the propylene oxide, most of the acids and about 20% of the solvent is fed through line 25 to distillation column 26. In this column propylene oxide and lower boiling components such as propylene, propane, acetaldehyde, methyl formate, and a small amount of residual CO2 are removed overhead, and water, acids, methanol, acetone, methyl acetate and residual solvent are removed as bottoms. The processing of this bottoms stream to recover the residual solvent and such commercially valuable by-products as acetic -acid or other acid values will be discussed below. Column 26 is heated to approximately 40 C. at the top and 210 C. at the bottom and operates at p.s.i.a. Forty plates are used with a reiux ratio of 0.16.

The overhead stream from column 26 is fed through line 27 to a C3 removal column 28. This column is heated to about 50 C. at the top and 160 C. at the bottom and maintained at 300 p.s.i.a., and propylene, propane and any residual CO2 are removed overhead; propylene oxide, acetaldehyde and methyl formate are removed as bottoms. Thirty-four plates and a reflux ratio of 0.31 are used. The overhead from this column is fed through line 29 to a propane-propylene splitter column 30. This column is heated to approximately 50 C. at the top and 55 C. at the bottom under 300 p.s.i.a. Seventy-five plates and a yreiiux ratio of 11.7 are utilized. Propane is removed from the bottom through line 34 and propylene is taken overhead through line 35 and recycled to the reactor. Some propane may be driven overhead, if desired, for recycle by increasing the temperature at the bot r tom of this column.

An alternative procedure for removing propane from recycle propylene is to combine the overhead from column 28 with the overhead stream in line 16 from condenser 15 leading to absorber 20. As mentioned previously, the liquid bottoms from the absorber containing solvent, propylene and propane may be recycled directly to the reactor or further processed for propylene purification, i.e., propane removal. When the concentration of propane in the reactor tends to build up to a level which interferes with the propylene oxidation, additional, or excess, propane is prevented from being recycled to the reactor by directing the eliiuent from absorber 20, Wholly or partially, through a side-stream taken from line 44, e.g., by means of a distributing valve into a desorber operated at about 50 C. at the top and 100 C. at the bottom and 300 p.s.i.a. pressure. Here, solvent is removed as bottoms and recycled to the reactor through line 44, and propane and propylene are removed overhead to a C3H6-C3H8 splitter operating at 300 p.s.i.a. and heated to about 50 C. at the top and 55 C. at the bottom. Propane is removed as bottoms and propylene of essentially the same composition as the initial feed material is recycled to the reactor propylene feed stream.

The bottoms stream from column 28 containing propylene oxide, acetaldehyde and methyl formate is fed through line 31 to distillation column 32 for acetaldehyde removal. This column, heated to about 50 C. at the top and 60 C. at the bottom, operates at 33 p.s.i.a. pressure and utilizes 89 plates at a reflux ratio of 39. Acetaldehyde is removed overhead through line 36.

Bottoms from column 32 containing methyl formate and propylene oxide are removed through line 37 to a methyl formate removal zone 38. In the present embodi- 50 plates and operating at C. at the top and 47 C. at the bottom. As entraining agent a hydrocarbon solvent boiling above 67 C. is used. In the present embodiment normal heptane, the preferred paraffin, is used. The entraining agent should have a boiling point of at least 35 C. above that of methyl formate.

Other parafiinic hydrocarbons suitable for use as entraining agents in column 3S include both individual parains having from 6 to 18 carbon atoms and mixtures thereof. Exemplary paraliins include straight chain paras hexane, octane, nonane, decane, dodecane, pentadecane and octadecane. Suitable branch chain isomers of paraflins boiling above n-hexane include 2- and S-methyl hexanes, 2,2-, 2,4- and 3,3-dimethyl pentanes, 3-ethyl pentane, 2,2,3-trimethyl butane, 2,2,3,3tetramethyl butane, 2,2,3, 2,2,4, 2,3,3- and 2,3,4-trimethyl pentanes, 2-methyl-3-ethyl pentane, 2,3-dimethyl hexane, 3,4-dimet'nyl pentane, 2, 3- and 4-methyl heptanes, 2- methyl nonane, 2,6-dimethyl octane, 2,4,5,7tetramethyl octane and the like. l

In addition to straight and branch chain paraiiins, mixtures of such parafiins are suitable herein. For example, various paraffmic naphthas are suitable. Typical parafnic naphthas include selected fractions of straight-run gasolines and kerosenes. Other parainic naphthas include selected hydrogenated fractions of polygas and other low molecular weight propylene polymers (e.g., propylene well as selected hydrogenated and alkylated fractions of naphthas obtained from thermal cracking and catalytic crackingof gas oils. Still other parafiinic naphthas include selected fractions of Udex raliinates (derived from solvent extractions using, e.g., diethylene glycol) from various reforming operations. For example, a particularly suitable parafiinic naphtha useful as entraining agent in the extractive distillation separation of propylene oxide from methyl formate is a Cq-Cs fraction of Udex raffinate. The paraffnic naphthas used herein may contain small amounts of naphthenes, olefins and aromatics derived from reforming operations Without adverse effects; however, for best results these associated hydrocarbons should not exceed about 15 weight percent based on said naphtha.

The selection of a particular parafiinic hydrocarbon entraining agent will depend primarily upon the boiling points of the particular epoxide and oxygenated impurities associated therewith.

As noted above, the acyclic parafiinic hydrocarbons suitable as ext-ractants in column 38 are those having a boiling point at lea-st 35 C. higher than the boiling point of the particular impurity(s) boiling within 5 C. of the olefin oxide in a crude mixture containing oxygenated impurities. These hydrocarbons, moreover, should boil at no less than 67 C. In general the upper 4boiling point of hydrocarbon solvents used is limited only by practical engineering considerations. A preferred boiling point range for hydrocarbons -used herein is from 67 C. t0 250 C.

Use of the entraining agents as defined herein in the extractive distillation separation of olefin oxides has numerous superior features, eg., increased sepa-ration enhancement, ease of separation of the olefin oxide from the entraining agent, freedom from corrosion problems and econom In a typical operation, the crude feed containing the olefin oxide to be separated and purified and oxygenated impurities associated therewith is fed to an intermediate point of the extractive distillation column. The parafiinic hydrocarbon entraining agent is fed to a higher region of the col-umn. The column is heated by means of a reboiler at the base thereof. The overhead vapors from the column comprise essentially all of the oxygenated impurities boiling Within 5 C. of the olen oxide. These vapors are condensed and reliuxed to the column While a portion is removed as distillate product. Bottoms from the column comprising essentially the parafnic hydrocarbon entraining agent containing the olefin oxide are Withdrawn through a reboiler and fed to an olefin oxide refining column Where the olefin oxide is stripped from the entraining agent and taken overhead in purified form. The entraining agent is removed as bottoms from the olefin oxide refining column and continuously recycled to the extractive distillation column.

The ratios of paraflinic hydrocarbon to crude feed are not critical herein and may be varied considerably. For example, ratios of 1:1 to 15:1 may suitably be used, although ratios Within the range of 5:1 to 10:1 are preferred.

Temperatures and pressures used in the extractive distillation column may be variedover wide ranges. In general, temperatures at the reboiler should be such that the olefin oxide content in the entraining agent Withdrawn as bottoms will be maintained at a maximum. Preferably, the column is operated at atmospheric pressures although subatmospheric and superatmospheric pressures may also be used.

In the present embodiment, the entraining agent, normal heptane (weight solvent ratio=9.5) is fed to column 38 through line 39. Methyl formate is removed overhead through line 40 and a normal heptane-propylene oxide mixture is removed from the bottom through line 41 to distillation column 42 for propylene oxide refining.

Although the present embodiment describes an extractive distillation separation of methyl formate and propylene oxide, it is contemplated that this separation can also be accomplished by other means such as solvent extraction, azeotropic distillation, adsorption and desorption, complex formation, etc.

Column 42 is heated to about 35 C. at the top and about C. at the bottom. This column has twentyfive plates and operates at a reflux ratio of 5.0 under a pressure of 15 p.s.i.a. Heptane is Withdrawn from the bottom and recycled via line 43 to extractive distillation column 38. Propylene oxide of 99-l-% purity is withdrawn through line 48 as final product.

Turning now to the recovery of other valuable oxyigenated products, reference is made to the bottoms stream from primary product splitter 26. This stream containing solvent, acid values, Water and intermediate lboilers such as acetone, methyl acetate, methanol, iso- `propanol and allyl alcohol is fed through line 50 to solvent-acids splitter 51. From this column, operated at :about 105 C. at the top and 192 C. at the bottom under v15 p.s.i.a. pressure and a reux ratio of 3.0 and utilizing 10 plates, most of the residual solvent is removed as bottoms and recycled to the absorber. An overhead stream containing the remaining residual solvent, water, acid `values and intermediate boilers is directed to distillation Icolumn 54 from which the intermediates are taken overhead. Column 54 utilizes 60 plates and operates at about 288 C. at the top and 116 C. at the bottom under 15 p.s.i.a. pressure and a reflux ratio of 8.0.

Bottoms from column 54 containing primarily water, :acetic acid and formic acid and a small amount of residual :solvent are directed through line 56 to azeotropic distilla- Ation column 57. This column contains about 70 trays and 'operates at about 77 C. at the top and 125 C. at the bottom under 15 p.s.i.a. pressure. Benzene is used as an :azeotrope-former and is fed through line 61 to the column at a point above the top tray at a ratio of 9 parts by `Weight of benzene for each part of column overhead prod- `ruct. Uniquely, in this system benzene forms two distinct :azeotropic mixtures; one with water and one with forrnic acid, rather than a ternary azeotrope of these three components. In operation, a benzene-water azeotrope and a '.-benzene-formic acid azeotrope are removed overhead 'through line 58 to a condenser (circulating water). Upon condensing, a mixture of benzene, water and formic acid :are passed to collector 59' wherein the mixture separates into an upper benzene phase and a lower phase containing water and formie acid. The latter two components are removed from the bottom of the collector while benzene from the upper phase (replenished with make-up benzene `through line 60) is recycled to the azeotropic distillation column.

Meanwhile, acetic acid, which does not azeotrope with benzene in column 57, is removed as bottoms from this column through line 62 together with small amounts of .residual solvent from the main oxidation reactor to an :acetic acid refining column 63 having 40 trays and operated at about 118 C. at the top and 130io C. at the 'bottom under l5 p.s.i.a. pressure and a reflux ratio of 5. Purified acetic acid is removed overhead while the residual oxidation solvent is recycled through line 64 to the oxida- '.tion reactor 11 -via absorber 20.

ln a typical oxidation according to the present embodi- :ment feed materials are added to reactor 11 at approxi- Vmately the following hourly rates: propylene, 530 g., Oxy- ;gen, 270 g. and solvent (c g., propylene glycol diacetate), -4600 g. At steady state (reactor residence time about 4.0 iminutes) propylene conversion is about 28% and oxygen conversion is 99.9%. Among the primary oxidation prod- Vucts propylene oxide is obtained in about 39% yield and acetic acid about 9% yield, together with minor amounts of other oxygenated products.

Example 2 This example illustrates a modification of the present process wherein the hydrocarbon oxidation may be controlled to alter the ratios of the more important products on demand. In this example the propylene oxidation is controlled to yield a higher ratio of acetic acid relative to propylene oxide, whereas the reverse case was described in the foregoing example.

The procedure outlined in Example 1 is followed except that conditions are selected which, from experience, are known to produce a low propylene oxide-acetic acid ratio, e.g., 0.8. The CgH/OZ molar feed ratio is initially set at about 1.0, the temperature in the reactor is 170 and pressure 850 p.s.i.g. The reactor contents are mixed with a Dispersimax agitator operating at 1500 r.p.m. At steady polyhydroxyallranes, polyhydroxycycloalkanes,

state, reactor residence time about 8 minutes, propylene conversion is about 40%. The residue content in the reactor efuent contains about 32 wt. percent and the residue content in the solvent recycle stream 35 wt. percent based on total streams. Under these conditions there is an insufficient amount of residue present in the reactor to be oxidized to acetic acid to produce the above desired propylene oxide-acetic acid ratio.

Therefore, the recycle solvent composition is adjusted so as to increase the residue content in the recycle solvent, and hence the reactor. Accordingly, the residue purge is appropriately decreased by reducing the amount of recycle solvent fed to the residue removal column. Upon reaching steady state the residue in the recycle solvent has increased to a level equivalent to the amount of residue required in the reactor. Propylene oxide is obtained in about 20 mole percent yield and acetic acid in approximately 25 mole percent yield based on propylene reacted, together with minor amounts of other oxygenated products.

The reaction products in this example are recovered in the same separation system described above.

Solvent losses due to mechanical operation of the process are made up by adding fresh solvent to the system as needed, preferably, to the line entering the absorber.

It will be seen, therefore, that the residue content in the solvent recycle stream and, hence, the reactor, can be adjusted to any suitable level by use of a residue removal column operating on the recycle solvent and thus control the course of the oxidation.

In general, propylene oxide-acetic acid ratios may be produced within the range of from about 0.511 to 5.521. For each P.O./acetic acid ratio Within this range, of course, a definite residue level or concentration in the reactor is required.

The above examples illustrate the control and flexibility achieved by the instant hydrocarbon oxidation and product recovery system.

While the invention has been specifically described with reference to the oxidation of propylene and recovery of valuable oxygenated products including propylene oxide, acetic acid, acetaldehyde, methyl formate, etc., it is within the purview of the invention to utilize the above-described and illustrated system for the oxidation of other olenic compounds and recovery of oxygenated products corresponding to or similar to those described above. It being understood that process conditions, e.g., temperatures and pressures in the reactor, flasher, stripper, columns, etc. will be modified `accordingly to make the necessary separations.

Other olefins suitable for use herein preferably include those of the ethylenic and cycloethylenic series up to 8 carbon atoms per imolecule, e.g., ethylene, propylene, butenes; pentenes, hexenes, heptenes and octenes', cyclobutenes, cyclopentenes, cyclohexenes, cyclooctenes, etc. Of particular interest, utility and convenience are acyclic olefins containing from 2 to 8 carbon atoms. Included are the alkyl-substituted oleins such as 2-methyl-1-butene, 2- methyl-Z-butene, Z-methyl-propene, 4-methyl-2-pentene, 2,3-dimethyl-2-butene and Z-methyl-Z-pentene. Other suitable olenic compounds include dienes such as butadiene, isoprene, other pentadienes and hexadienes', cyclopentenes, cyclohexenes, cyclopentadiene, vinyl-substituted cycloalkenes and benzenes, styrene, methylstyrene, and other vinyl-substituted aromatic systems.

It is to be understood that the foregoing detailed description is merely illustrative of the invention and that many variations will occur to those skilled in the art without departing from the spirit and scope of this invention.

We claim:

1. Process for the production of oxygenated organic compounds which comprises oxidizing propylene feedstocks with molecular oxygen in a solvent selected from the group consisting of fully esteried polyacyl esters of Polystycols and mixtures thereof, wherein said esters contain from 1 2 to 18 moiety, under temperatures and cause the reaction to recovering said oxygenated products by:

carbon atoms in each alkylene and cycloalkylene pressures suilicient to proceed in the liquid phase, and

(a) directing an eilluent stream of the reaction mixture from a reaction zone through a combination letdown distillation zone comprising a flashing zone followed by a stripping zone into which the bottoms from said flashing zone is directed, said flashing zone and stripping zone being maintained at pressures substantially lower than in each preceding zone and in said reaction zone and at temperatures necessary to separate substantially all of the low and intermediate boiling products overhead as gas phase and higher boiling components including the bulk of the solvent and polymeric residue having a boiling point above that of said solvent which are removed as bottoms from said stripping zone,

(b) passing said gas phase to condensing zones, from whence uncondensed gases are directed -to an absorbing zone into which eluent solvent from said stripping zone is `also passed to absorb uncondensed propylene and propylene oxide,

(c) directing a side-stream of said eiliuent solvent in V(b) through a residue removal distillation zone wherein the polymeric residue content in said solvent is purge regulated to admit sufiicient polymeric residue into said reaction zone as to achieve a polymeric residue concentration corresponding to that required for a desired product distribution, and wherein excess polymeric residue is removed as bottoms and solvent is distilled overhead and recombined with the solvent bottoms from said stripping zone and fed to said absorbing zone,

(d) passing a combined stream of condensed liquids from said condensing zones into a primary products distillation zone where organic acids, water, intermediates and residual solvent are removed as -bottoms and propylene oxide, propylene, propane, acetaldehyde and methyl formate are distilled overhead,

(e) directing the overhead from (d) to a C3 removal distillation zone Where propylene and propane are distilled overhead and propylene oxide, acetaldehyde and methyl formate are removed as bottoms,

(f) passing said bottoms from said C3 removal zone to a distillation zone where acetaldehyde is distilled overhead and propylene oxide and methyl formate are removed as bottoms,

(g) passing the bottoms from (f) to an atmospheric extractive distillation zone using as extractive solvent a hydrocarbon solvent boiling above 67 C. and wherein methyl formate is removed overhead and said extractive solvent containing propylene oxide is removed `as bottoms,

occurs at temperatures within the to 400 C. and pressures within the range of 0.5 to 350 atmospheres.

(h) feeding the bottoms from (g) to a propylene oxide refining distillation zone from which puried propylene oxide is distilled overhead and recovered, while said hydrocarbon solvent is removed as bottoms and recycled to said extractive distillation zone,

(i) feeding the bottoms from said acids separation distillation zone in step (d) to an acid-solvent distillation splitting zone where most of the residual solvent from said reaction Zone not removed in said hashing and stripping zones is removed as bot-toms and recycled to said absorber,

(j) feeding the overhead from said acid-solvent distillation splitting zone to an acid-intermediates distillation zone where isopropanol, allyl alcohol, methanol and other intermediate boilers and some water are recovered overhead, while directing the bottoms from said acid-intermediates distillation zone to an azeotropic distillation column using benzene as an azeotrope-former for water and formic acid,

`(k) removing from said azeotropic distillation zone an overhead stream containing a mixture of benzenewater and benzene-formic acid azeotropes to a condensing zone wherein benzene is separated from water and formic acid and feeding these three components to a collecting zone in which benzene forms an upper phase from which benzene is returned to said azeotropic distillation zone, while water and formic acid are removed as a lower phase, and

(l) removing from said azeotropic distillation zone a bottoms stream containing acetic acid and a small amount of residual solvent to a distillation refining zone wherein purified acetic acid is recovered overhead and said residual solvent is removed as lbottoms and recycled to said absorber.

2. Process according to claim 1 wherein said oxidation range of from 50 C.

3. Process according to claim 2 wherein said solvent comprises propylene glycol diacetate.

4. Process according to claim 3 wherein said oxidation occurs at temperatures within the range of from 140 C. to 250 C. and pressures within the range of from 5 to 200 atmospheres.

References Cited UNITED STATES PATENTS 3,024,170 3/ 1962 Othmer et al. 203-67 3,097,215 7/ 1963 Courter et al. 203-42 3,153,058 10/ 1964 Sharp et al. 260-348.5 3,165,539 1/11965 Lutz 203-42 3,207,677 9/'1965 Colton 203-88 3,254,962 -6/1966 (Fox et al. 203-42 WILBUR L. BAscoMB, JR., Examiner.

NORMAN Y'UDKOFF, Primary Examiner.

P04050 UNITED STATES PATENT OFFICE 569) CERTIFICATE 0F CORRECTION Pltent N0. 3 .350 ,H2l Dated October 31.- 1157 Invgnmru) Robert C. Binning et al It is certified that error appears in the above-identified patent and :het said Lettere Patent are hereby corrected as shown below:

Column l, line 5l, "products(s)" should be products Column 2, line 3, "feasibly" should be feasible Column 2, lines 25 and 26, "have been described (U.S. patents solvent systems have been described (U.S. patents" should be have been described (U.S. patents Column 15, line 73, "in the reactor is 170 and" should be in the reactor is 170C and Signed and sealed this 22nd day of June 1 971 (SEAL) Attest:

EDWARD M.`FLETCHER,JR. WILLIAM E. SCHUYLER, J'R. Attesting Gfficer Commissioner of Patents 

1. PROCESS FOR THE PRODUCTION OF OXYGENATED ORGANIC COMPOUNDS WHICH COMPRISES OXIDIZING PROPYLENE FEEDSTOCKS WITH MOLECULAR OXYGEN IN A SOLVENT SELECTED FROM THE GROUP CONSISTING OF FULLY ESTERIFIED POLYACYL ESTERS OF POLYHYDROXYALKANES, POLYHYDROXYCYCLOALKANES, POLYGLYCOLS AND MIXTURES THEREOF, WHEREIN SAID ESTERS CONTAIN FROM 1 TO 18 CARBON ATOMS IN EACH ACYL MOIETY AND FROM 2 TO 18 CARBON ATOMS IN EACH ALKYLENE AND CYCLOALKYLENE MOIETY, UNDER TEMPERATURES AND PRESSURES SUFFICIENT TO CAUSE THE REACION TO PROCEED IN THE LIQUID PHASE, AND RECOVERING SAID OXYGENATED PRODUCTS BY: (A) DIRECTING AN EFFLUENT STREAM OF THE REACTION MIXTURE FROM A RACTION ZONE THROUGH A COMBINATION LETDOWN DISTILLATION ZONE COMPRISING A FLASHING ZONE FOLLOWED BY A STRIPPING ZONE INTO WHICH THE BOTTOMS FROM SAID FLASING ZONE IS DIRECTED, SAID FLASHING ZONE AND STRIPPING ZONE BEING MAINTAINED AT PRESSURES SUBSTANTIALLY LOWER THAN IN EACH PRECEDING ZONE AND IN SAID REACTION ZONE AND AT TEMPERATURES NECESSARY TO SEPARATE SUBSTANTILLY ALL OF THE LOW AND INTERMEDIATE BOILING PRODUCTS OVERHEAD AS GAS PHASE AND HIGHER BOILING COMPONENTS INCLUDING THE BULK OF THE SOLVENT AND POLYMERIC RESIDUE HAVING A BOILING POINT ABOVE THAT OF SAID SOLVENT WHICH ARE REMOVED AS BOTTOMS FROM SAID STRIPPING ZONE, (B) PASSING SAID GAS PHASE TO CONDENSING ZONES, FROM WHENCE UNCONDENSED GASES ARE DIRECTED TO AN ABSORBING ZONE INTO WHICH EFFLUENT SOLVENT FROM SAID STRIPPING ZONE IS ALSO PASSED TO ABSORB UNCONDENSED PROPYLENE AND PROPYLENE OXIDE, (C) DIRECTING A SIDE-STREAM OF SAID EFFLUENT SOLVENT IN (B) THROUGH A RESIDUE REMOVAL DISTILLATION ZONE WHEREIN THE POLYMERIC RESIDUE CONTENT IN SAID SOLVENT IS PURGE REGULATED TO ADMIT SUFFICIENT POLYMERIC RESIDUE INTO SAID REACTION ZONE AS TO ACHIEVE A POLYMERIC RESIDUE CONCENTRATION CORRESPONDING TO THAT REQUIRED FOR A DESIRED PRODUCT DISTRIBUTION, AND WHEREIN EXCESS POLYMERIC RESIDUE IS REMOVED AS BOTTOMS AND SOLVENT IS DISTILLED OVERHEAD AND RECOMBINED WITH THE SOLVENT BOTTOMS FROM SAID STRIPPING ZONE AND FED TO SAID ABSORBING ZONE, (D) PASSING A COMBINED STREAM OF CONDENSED LIQUIDS FROM SAID CONDENSING ZONES INTO A PRIMARY PRODUCTS DISTILLATION ZONE WHERE ORGANIC ACIDS, WATER, INTERMEDIATES AND RESIDUAL SOLVENT ARE REMOVED AS BOTTOMS AND PROPYLENE OXIDE, PROPYLENE, PROPANE, ACETALDEHYDE AND METHYL FORMATE ARE DISTILLED OVERHEAD, (E) DIRECTING THE OVERHEAD FROM (D) TO A C3 REMOVAL DISTILLATION ZONE WHERE PROPYLENE AND PROPANE ARE DISTILLED OVERHEAD AND PROPYLENE OXIDE, ACETALDEHYDE AND METHYL FORMATE ARE REMOVED AS BOTTOMS, (F) PASSING SAID BOTTOMS FROM SAID C3 REMOVAL ZONE TO A DISTILLATION ZONE WHERE ACETALDEHYDE IS DISTILLED OVERHEAD AND PROPYLENE OXIDE AND METHYL FORMATE ARE REMOVED AS BOTTOMS, (G) PASSING THE BOTTOMS FROM (F) TO AN ATMOSPHERIC EXTRACTIVE DISTILLATION ZONE USING AS EXTRACTIVE SOLVENT A HYDROCARBON SOLVENT BOILING ABOVE 67*C. AND WHEREIN METHYL FORMATE IS REMOVED OVERHEAD AND SAID EXTRACTIVE SOLVENT CONTAINING PROPYLENE OXIDE IS REMOVED AS BOTTOMS, (H) FEEDING THE BOTTOMS FROM (G) TO A PROPYLENE OXIDE REFINING DISTILLATION ZONE FROM WHICH PURIFIED PROPYLENE OXIDE IS DISTILLED OVERHEAD AND RECOVERED, WHILE SAID HYDROCARBON SOLVENT IS REMOVED AS BOTTOMS AND RECYCLED TOS AID EXTRACTIVE DISTILLATION ZONE, (I) FEEDING THE BOTTOMS FROM SAID ACIDS SEPARATION DISTILLATION ZONE IN STEP (D) TO AN ACID-SOLVENT DISTILLATION SPLITTING ZONE WHERE MOST OF THE RESIDUAL SOLVENT FROM SAID REACTION ZONE NOT REMOVED IN SAID FLASHING AND STRIPPING ZONES IS REMOVED AS BOTTOMS AND RECYCLED TO SAID ABSORBER, (J) FEEDING THE OVERHEAD FROM SAID ACID-SOLVENT DISTILLATION SPLITTINGGZONE TO AN ACID-INTERMEDIATES DISTILLATION ZONE WHERE ISOPROPANOL, ALLYL ALCOHOL, METHANOL AND OTHERE INTERMEDIATE BOILERS AND SOME WATER ARE RECOVERED OVERHEAD, WHILE DIRECTING THE BOTTOMS FROM SAID ACID-INTERMEDIATES DISTILLATION ZONE TO AN AZEOTROPIC DISTILLATION COLUMN USING BENZENE AS AN AZEOTROPE-FORMER FOR WATER AND FORMIC ACID, (K) REMOVING FROM SAID AQEOTROPIC DISTILLATION ZONE AN OVERHEAD STREAM CONTAINING A MIXTURE OF BENZENEWATER AND BENZENE-FORMIC ACID AZEOTROPED TO A CONDENSING ZONE WHEREIN BENZENE IS SEPARATED FROM WATER AND FORMIC ACID AND FEEDING THESE THREE COMPONENTS TO A COLLECTING ZONE IN WHICH BENZENE FORMS AN UPPER PHASE FROM WHICH BENZENE IS RETURNED TO SAID AZEOTROPIC DISTILLATION ZONE, WHILE WATER AND FORMIC ACID ARE REMOVED AS A LOWER PHASE, AND (L) REMOVING FROM SAID AZEOTROPIC DISTILLATION ZONE A BOTTOMS STREAM CONTAINING ACETIC ACID AND A SMALL AMOUNT OF RESIDUAL SOLVENT TO A DISTILLATION REFINING ZONE WHEREIN PURIFIED ACETIC ACID IS RECOVERED OVERHEAD AND SAID RESIDUAL SOLVENT IS REMOVED AS BOTTOMS AND RECYCLED TO SAID ABSORBER. 